Production of phenazonium dyestuff images



Patented Oct. 10, 1950 PRODUCTION OF PHENAZONIUM DYESTUFF IMAGES Vsevolod Tulagin, Phillipsburg, N. a, and Willy A. Schmidt, Easton, Pa, assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application December 23, 1947, Serial No. 793,535

8 Claims.

The present invention relates to the production of blue to reddish-blue phenazonium dyestuff images by color development of an exposed silver halide emulsion with an orthophenylenediamine type developer in the presence of a color former which is a B-naphthol derivative.

Our copending application Serial Number 640,382, filed January 10, 1946, now Patent No. 2,486,440, of which the present application is a continuation in part describes the production of phenazonium dyestufi images by color developing an exposed silver halide emulsion with a color developer comprising an ortho-phenylenediamine type developer in the presence of various color formers. Among the color formers mentioned are those containing a phenolic hydroxyl group which couples in para. position to such group. It has been observed that with such color formers, the most common color of the dyestuff images obtained is either red or that shade of red known in the photographic artas.

magenta. As a matter of fact, it may be said that these are the only shades Which areobtainable from phenols or naphthols when the coupling reaction takes place para to the phenolic hydroxyl group. This limitation on the shades of the dyestuffs produced according to the method of said application imposes a restriction on its use in three-color photography.

It has now been discovered that phenazonium dyestufi images having a bluish shade, i. e., a

shade ranging from blue to reddish-blue are obtained by color developing an exposed silver halide emulsion with an ortho-phenylenediamine type developer in the presence of a fl-naphthol containing an amino Qrsubstituted amino group. 2 i The production of phenazonium dyestuif images by the utilization of such color formers and silver halide emulsions and color developers containing such color formers constitutes the purposes and objects of the present invention.

The ,B-naphthol compounds contemplated for employment herein may be represented by the following structural formula:

sulfonyl, and the like, and Z is an alkyl radical as above or halogen, i. e., chlorine, bromine, or the like, a sulfonic acid group, or hydrogen.

Examples of compounds embraced by this formula and which we have found to be eminently suitable in yielding the desirable blue images by color development with an orthophenylenediamine type developer are the following:

. 7-amino-2-naphthol.

. 7 -acetamido-2-naphthol.

. 7-benzoylamido-2-naphthol.

. 7-benzene sulfonylamido-2-naphthol. 7-methanesulfonylamino-2-naphthol. 7-anilino-2-naphthol.

. 7 -anisidino-2-naphthol.

. S-amino-Z-naphthol.

. B-acetamido-Z-naphthol.

10. 8-N-benzyl-benzoylamido-2-naphthol. ll. 5-acetamido-2-naphthol.

12. 3-anilino-2-naphthol.

13. 7-ethylamino-2-naphthol.

S-stearoyl sulfonylamido-2-naphthol. 8-amino-2-naphthol5sulfonic acid. 5-amino-2-naphthol-7-sulfonic acid. .17. 5-chloro-8amino-2-naphthol.

'18. 7-stearoylamido-2-naphthol.

These compounds are, for'the most part, known in the literature, and in any casecan be made by simple and well known chemical reactions, such as amidation, alkylation, halogenation, and the like. A description of the method of preparing the compounds is accordingly deemed to be unnecessary.

The color formers may be employed either in the emulsion or in the developer. However, where they contain a group preventing diffusion, in which case they are preferably used in the emulsion. Examples of compounds falling within such category are those in which the nitrogen atom is substituted by an aliphatic radical containing at least locarbon atoms, i. e., stearyl, and the like i The color developers which are employed are, as stated, of the ortho-phenylenediamine type, anumber of examples of which are referred to in the aforesaid Schmidt and Tulagin application.. Suitable developers of this class are; 7

4i-6-dia1iilino metanilic acid 4.6 bis (p methoxy phenylamino) met anilic acid 4 (o methoxy phenylamino) 6 (pmethoxy-phenylamino) metanilic acid I 4.6-bis-(o-methoxy phenylamino) metanilic acid 4 (p sulfo phenylamino) 6 dimethylamino metanilic acid, and the like.

The invention may be effectuated so as to use the color developing method for producing colored negatives, colored positives, or reverse images. These general methods are conventional in the art, being dependent for their efficacy upon the point at which color development takes place.

The invention is further illustrated by the following examples, but it is to be understood that the invention is not restricted thereto.

Example 1 A photographic silver bromide emulsion is exposed and color developed in the following developer:

4.6-dianilino metanilic acid grams 1.5 Sodium sulfite (anhydrous) do 60 Potassium carbonate (anhydrous) do 40 Pyridine cubic centimeters 12 7-amino-2-naphthol grams 1 Water cubic centimeters 1000 After development the film is washed for 15 minutes, the silver removed by the conventional ferricyanide bleach, and then fixed and washed. There is thus obtained a brilliant blue phenazonium dyestuff image.

Example 2 The developer is the same as in Example 1 excepting that there is used 'l-acetamido-2- naphthol in lieu of the 'l-amino-2-naphthol.

By processing the exposed silver halide emulsion as in Example 1 a blue phenazonium dyestufif image is obtained.

Example 3 A silver halide emulsion is exposed, developed in a black and white M-Q developer, re-exposed, and developed in a developer of the following composition:

4.6-dianilino metanilic acid grams Sodium sulfite (anhydrous) do 60 Potassium carbonate (anhydrous) do 40 Pyridine cubic centimeters 12 'l benzoylamido-2-naphthol grams 1 Water cubic centimeterse- 1000 The film is washed for 15 minutes, the silver bleached with a'ferricyanide bleach, fixed and washed. A blue phenazonium dyestufl image is thereby produced.

Example 4 4-;6"-dianilino .metanilic' acid. grams Sodium sulfite do 60 Potassium carbonate do.. .40 Pyridine cubic centimeters 12 Water do 1000 The film is then washed, bleached and fixed the conventional manner to yield a blue phenazonium dyestuif image.

The following table lists the color of the phenazonium dyestufi' images obtained when employing the developer of Example 4 with other color forming components of the fi-naphthol class here involved:

Table .1

Color of Formed Coupler Dye 7-benzenesulionylamido-2-napthol Bluish violet. 7-auilino-2-naphthol B 7-anisidino-2-naphth0l Do. S-amino-Z-naphthol. Do. S-acetamido-Z-naphthol. Do. S-N-benzyl-benzoylamido-2-napl1tho Do. S-acetamido-Z-napht Do. 3-anilino-2-naphthol Do.

Various modifications of the invention will occur to persons skilled in the art, and we therefore do not intend to be limited in the patent granted except as necessitated by the prior art wherein R is a member selected from the class consisting of'hydrogen, alkyl and aromatic radicals, R1 is selected from the class consisting of hydrogen and acylamino, and Z is a member selected from the class consisting of hydrogen, halogen, alkyl and sulfo groups Z being in the ring 'fused to that containing the phenolic hydroxyl group.

2 The process as defined in claim 1 wherein the color former is 'l-amino-Z-naphthol.

3. The process as defined in claim 1 wherein the color former is 'l-benzoylamido-Z-naphthol.

4. A photographic silver halide emulsion containing as a color former capable of yielding bluish phenazonium dyestuff images when color developed with an ortho-phenylenediamine type developer a compound of .the followin formula:

wherein R is a member selected from the class consisting of hydrogen, alkyl and aromatic radicals, R1 is selected from the class'consisting of hydrogen and acylamino, and Z is a member selected from the class consisting of h'ydrogen, halogen, alkyl and sulfo groups .Z'Sblllgill the ring fused to that containing the phenolic hydroxyl group.

5. A photographic developer containing an ortho-phenylenediamine compound and as a color former capable of yielding'bluish phenazonium dyestuif images a compound of the following formula 5 6 wherein R is a member selected from the class oped with an ortho-phenylenediamine type deconsisting of hydrogen, alkyl and aromatic radiveloper 7-stearoylamino-2-naphthol. cals, R1 is selected from the class consisting of hydrogen and acylamino, and Z isa member selected from the class consisting of hydrogen, 5 halogen, alkyl and sulfo groups Z being in the ring fused to that containing the phenolic hy- REFERENCES CITED .droxyl gr up, S Compound being e from The following references are of record in the groups rendering said compound non-diffusing in m f this patent; photographic emulsions. 10

6. A photographic developer capable of yield- UNITED STATES PATENTS ing bluish phenazonium dyestuff images compris- Number Name Date ing 4.6-dianilino metanilic acid and 'I-amino-Z- 2,356,475 Schinzel Aug. 22, 1944 naphthol. 2,394,527 Woodward Feb. 5, 1945 7. A photographic developer capable of yielding 15 2,441,491 Kendall et a1. May 11, 1948 bluish phenazonium dyestufl images comprising 2,445,252 Tulagin July 13, 1948 4.6-dianilino metanilic acid and 7-benzoylamido- 2 naphtho1 FOREIGN PATENTS 8. A photographic silver halide emulsion con- Number Country Date taining as a, color former capable of yielding bluish 531,312 Great Britain Jan. 1, 1941 phenazonium dyestutf images when color devel- 536,939 Great Britain June 3, 1941 

1. THE PROCESS OF PRODUCING BLUISH PHENAZONIUM DYESTUFF IMAGES BY COLOR FORMING DEVELOPMENT WHICH COMPRISES EXPOSING A SILVER HALIDE EMULSION AND DEVELOPING THE SAME WITH AN ORTHOPHENYLENEDIAMINE TYPE DEVELOPER IN THE PRESENCE OF A COLOR FORMER HAVING THE FOLLOWING FORMULA: 